CN1150240C - Rigid polyurethane foam and its heat insulating construction element - Google Patents

Abstract

A rigid polyurethane foam is described which is preferably, while not exclusively, used for manufacturing composite building elements used in buildings or for manufacturing industrial constructions. The foam has a structure consisting of closed cells substantially free therein of optionally halogenated hydrocarbon foaming agents, having an adhesion strength to a supporting substrate, measured according to standards EN 1607, equal to or higher than 0.7 kg/cm2. The polyurethane foam may be obtained starting from at least one polyol and at least one isocyanate compound by using a water-based foaming agent entirely compatible with the strictest environmental requirements, and has good mechanical characteristics, characteristics of dimensional stability, characteristics of adhesion to a supporting substrate and, possibly, characteristics of fire resistance.

Description

Rigid urethane foam and heat insulating construction element thereof

Technical field

First aspect, preferably but not uniquely, the present invention relates to a kind of rigid urethane foam, it is used for being manufactured on the composite architectural materials that buildings uses, or the process industry structures.

Second aspect the present invention relates to comprise or be lined with the heat insulating construction element of described porous plastics, such as be used to prepare heat is ventilated or air-conditioning system with composite sheet, the curtain wall of pipeline, be used to make civilian or industrial building coiled material; Also relate to the thermal insulating material that suitably is lined with described porous plastics,, or be used for the wall of civilian or industrial building such as the wall that is used for refrigerating installation or refrigerating chamber.

Another aspect the invention still further relates to a kind of method of making aforementioned material of construction.

Prior art

As everyone knows, rigid urethane foam is a foamed polymer, under the situation that suitable kicker exists, by (for example comprising plural oh group, the compound of polyvalent alcohol) more than one prepares with polymerization addition mechanism with more than one the compound that comprises plural isocyano-group, the existence that wherein needs whipping agent to be being formed with the foaming structure that is made of closed porosity, thereby can obtain excellent thermal insulation properties.

Outside this character, simultaneously, rigid urethane foam must possess suitable binding property, good mechanical property (such as low fragility), low-thermal conductivity to the member-support base of the material of construction of manufacturing, if and specific end use arranged, also need to possess excellent dimensional stability with respect to temperature variation, and/or resistivity against fire.

Just by using halohydrocarbon, i.e. chlorofluorocarbon (CFC) class whipping agent and obtaining still, many-sidedly in recent years shows that this compounds is to make the ozonosphere that avoids ultraviolet radiation of preserving our planet be subjected to the corrosive major cause to all these performances before the several years.

CFC is owing to the potential loss of ozonosphere being banned usefulness, need to adopt a kind of alternate kicker, wherein recently some hydro carbons obtains to use widely, such as potential loss is lower than Skellysolve A or pentamethylene and the hydrogenated chloride fluorine hydrocarbon (HCFC) of CFC to ozone.

But still also there is the use restriction so far in this type of alternate kicker.

In fact, the hydro carbons kicker on the one hand, is applicable to existing foam device, on the other hand, and very easily combustion under specific concentrations, and easily form volatile mixture, this only can use them under the security measures of strictness, and only uses in some cases.For example, the hydro carbons kicker seldom is applied in the manufacturing of composite sheet, wherein porous plastics is located between the two metal sheets material as sandwich-type, is contained in hydrocarbon fuel in the porous plastics microvoid structure because the spark that cutting and forming operation produce can cause, easily produces dangerous.

In addition, adopt the thermal insulation properties of porous plastics in all purposes of hydro carbons kicker all bad, and thermal insulation is an important index.

Adopt hydrogenated chloride fluorine alkyl foaming (HCFC) catalyzer, itself make urethane foam possess required machinery, bonding, dimensional stability and thermal insulation properties really, on the contrary, because cost is too high, and owing to its title and close its commercial applications that makes of those halons of forbidding because of environmental issue are restricted.

In order to change this situation, once attempted water as whipping agent, because the hydrogen that is present in the water molecules is acid, can react with isocyanate compound.

More particularly, according to reaction of high order mechanism, water and isocyanate compound reaction, wherein, unsettled carboxylamine forms subsequently and decomposes, in reaction, form intermediary gaseous state carbonic anhydride (it generates effective whipping agent on the spot) and amine and react with other isocyanate groups successively, cause formation to comprise disubstituted urea group compound.

Though the cost of water is low and use unrestrictedly, water allows of no optimist as the trial of whipping agent up to now.

In fact, experimental study shows, the porous plastics that water obtains as whipping agent is frangible, under the differing temps size instability and, it is essential, not enough to the binding property of its support base.

The invention summary

On described technical problem basis, the invention provides a kind of rigid urethane foam of improvement, it has overcome defective described in the prior art.

According to a first aspect of the invention, the problems referred to above are resolved by a kind of rigid urethane foam, it is a foaming structure, the closed porosity of halohydrocarbon foaming agent constitutes this foaming structure by being substantially free of randomly, described porous plastics has bounding force to support base, secundum legem EN1607 measures, and is equal to or higher than 0.7kg/cm ²

In the following description book and claims, neither there is hydrocarbon blowing agents as described in term " porous plastics is made of the closed porosity that is substantially free of optional halohydrocarbon foaming agent " the expression porous plastics, also can not contains by using this hydrocarbon blowing agents to prepare the residue that porous plastics obtains.

The preferred embodiment of the present invention describes in detail

Urethane foam of the present invention is made up of two-phase system in fact, one of them, it is solid phase, the foaming structure that is made of closed porosity forms " honeycomb " structure, another is mutually for coming from the gas phase of whipping agent, be substantially free of optional halohydrocarbon foaming agent or its residue in the present invention, come from the CO that uses non-organic blowing agent such as water and obtain but preferably include ₂Or air.

Further, the percentage ratio of closed porosity is higher than 90% in the foaming structure of urethane foam of the present invention, and belongs to that class that is called as rigid urethane foam.

Preferably, in the scope of 70 ℃ of top temperatures, secundum legem EN1604 measures in minimum temperature-25 ℃, and the linear dimension unevenness percentage ratio of urethane foam of the present invention is not higher than 4%.

Especially, this feature makes porous plastics be applicable to all purposes, and such as the building board that is used to prepare heat ventilation or air-conditioning system usefulness pipeline, it needs dimensional stability good under the differing temps.

Preferably, urethane foam of the present invention, the fragility that secundum legem ASTM C421 measures, promptly weight loss percentage ratio is not higher than 3%.

This feature makes porous plastics be particularly suitable for all purposes, such as, can form tectum for building, the shock resistance that its outside need is good.

Preferably, urethane foam of the present invention, wherein the thermal conductivity of secundum legem ISO 6902 mensuration is 0.024-0.028W/m ℃, has identical good thermal insulation properties so that contain the material of construction of described porous plastics.

In order to realize the object of the invention, the high rigidity of required urethane foam closed pore structure is to obtain like this: at least a polyester and/or polyether glycol, it (for example has average functionality, hydroxy number in each molecule) is 2.5-8, and at least a isocyanate compound, its have average functionality (for example, in each molecule-NCO group number) be 2.5-3, the two reacts to each other.

More particularly, urethane foam of the present invention, by the also foaming acquisition simultaneously of mixture reaction with each component, each component is in per 100 weight part mixtures:

At least a polyester polyol of-10-25 part, its have minimum functionality be 2 and hydroxyl value be 250-600;

At least a isocyanate compound of-50-65 part;

The water base whipping agent of-1-2 part;

The appropriate surfactant of-0.3-2 part, it makes described at least a polyvalent alcohol and described isocyanate compound miscible mutually.

In the following description book and claims, term " hydroxy number " be used for representing the per unit weight measured according to standard A STMD1638 polyvalent alcohol can with the hydroxyl concentration of isocyanate groups reaction, unit is mgKOH/g.

In order to realize the object of the invention, the preferred polyester polyvalent alcohol is selected from the aryl polyvalent alcohol that molecular weight is 150-1600, is prepared such as the by product in can being produced by terephthalate.

Wherein, Shi Yi polyester polyol has following structural formula:

Wherein, R is an alkyl, and straight or branched has 1-5 carbon atom.

In the prescription of rigid urethane foam of the present invention, the functionality that described polyester polyol has be 3 and hydroxyl value be 400-600, preferably be about 500, the porous plastics of moulding will show excellent plasticity-, especially be fit to continuous processing and spraying method purposes.

Described polyester polyol have functionality be 3 and hydroxyl value be 300-400, and preferably be about 350, use and also can obtain same effect in the manufacturing processed in batches at continuous injection.

In the prescription of rigid urethane foam of the present invention, described polyester polyol have functionality be 4 and hydroxyl value be 300-400, and preferably be about 350, as an alternative, its advantage is to obtain quick crosslinked motion in initial forming step, promptly make the porous plastics of formation have three-dimensional structure, final hardness is not excessive simultaneously.This feature is specially adapted to the spray mo(u)lding method.

In the prescription of rigid urethane foam of the present invention, described polyester polyol have functionality be 5 and hydroxyl value be 450-550, and preferably be about 520, its advantage is to make the porous plastics of formation to have suitable bubble mobility and denseness.This feature is particularly useful in the batch forming operation.

Applicant's experiment shows, use the advantage of the described polyester polyol of above-mentioned consumption to be, reduced with the hardness of the urethane foam of water base whipping agent and isocyanate compound preparation, its fragility has also reduced thereupon, and the resistivity against fire of described porous plastics improves.

In order to realize the object of the invention, preferably, isocyanate compound is methylene radical two isocyanatos, and especially, and it is basically by being called polymeric MDI or " natural MDI " forms.The latter is made up of the mixture of methylene diisocyanate and several its oligopolymer basically, can be represented by following structural formula:

Wherein, n is the integer of 0-7.

Preferably, polymeric MDI comprises the methylene diisocyanate (n=0) of 40-55%, the oligopolymer of 15-30%, and the oligopolymer of wherein n=1, and 15-40%, wherein n is the integer of 2-7.

In order to prepare urethane foam of the present invention, preferably use superstoichiometric polymeric MDI.More specifically, the ratio between the amount of used isocyanic ester and the stoichiometric isocyanic ester or " isocyanate index " are higher than 1.1 (or percentage ratio is 110), and more preferably are higher than 1.2 (120%).

Because this technical characterictic, the applicant finds that the resistivity against fire of urethane foam and dimensional stability all are improved, and has promptly obtained a kind of more closely knit firm closed porosity three-dimensional structure.

In the preferred embodiment, aforesaid isocyanate index is 1.1 (110)-1.5 (150), more preferably is 1.2 (120)-1.5 (150), and more preferably is 1.4 (140)-1.5 (150).

Preferably, polymeric MDI of the present invention further comprises NCO isocyanate groups composition, is expressed as 30-32% with the parts by weight that account for whole molecular weight.

In order to realize purpose of the present invention, preferably use water base whipping agent, it is suitable for the liquid solution of the object of the invention for water or any other.

According to the present invention and by following detailed description, the particular combinations of starting ingredient can make a kind of hard expandable polyurethane porous plastics that makes water as whipping agent, it possesses excellent size stability under excellent thermal insulation properties, good mechanical property, the differing temps, and especially to the high adherence of support base, water base whipping agent of the prior art still fails to reach described performance.

In order to realize purpose of the present invention, aforementioned surfactants can be selected from anyly to be had the polar compound and makes polyvalent alcohol and isocyanate compound miscible compound mutually.

Preferably, tensio-active agent is selected from the silica-based surfactant that comprises fatty group or aryl chain, such as poly-(dimethyl siloxane) (PDMS) and poly-(phenyl methyl siloxanes), its viscosity is about 200-14000mPa*s in the time of 25 ℃, more preferably, its viscosity is about 2000-5000mPa*s in the time of 25 ℃.

Wherein, the preferred Silicon surfactant that uses has following structural formula:

Wherein, x and y are the integer of 0-70, and R is a polyether group, and it has following structural formula:

Wherein, m and n are the integer of 1-10.

In the prescription of rigid urethane foam of the present invention, described tensio-active agent has dual-use function: reduce original each other not miscible polyvalent alcohol and the isocyanate compound interfacial tension between the two, carry out required reaction; Stablize the microvoid structure of in type porous plastics, unless the polyurethane three-dimensional structure does not reach crosslinked level, and the stability of keeping certainly.

Valuably, tensio-active agent has been realized the structural uniformity that porous plastics is required by this way, and porous plastics is made of closed porosity basically.

Preferably, the consumption of tensio-active agent is the 0.5-1.5 weight part of per 100 parts of aforementioned each component mixtures.

In the preferred embodiment, rigid urethane foam of the present invention can be made by each component mixture that further comprises 0.1-4 part polyamines, particularly gathers 1,4-butyleneglycol base (PTMEG) diamines, its molecular weight is 425-625, and its viscosity is about 2500-5000mPa*s in the time of 25 ℃.

In order to realize the object of the invention, the preferred diamines that is shown below that also adopts valuably:

Wherein, n is the integer of 1-20, is preferably 4-6.

The applicant is surprised to find, by using aforesaid polyamines, porous plastics has improved significantly to the binding property of support base, like this in reaction feed and foaming step, make the control of processing parameter (for example, the temperature of reactant and/or support base) not too strict.

Especially, the applicant is surprised to find, by using aforesaid polyamines, urethane foam is higher than prior art significantly to the binding property of support base, and described prior art realizes as whipping agent by utilizing conventional polyurethane prescription and water.

This can prepare coating or valuably in conjunction with the material of construction of expansion urethane foam, and is that the material that whipping agent is made can be applicable to all purposes with water, comprises that processing parameter is difficult to control or uncontrollable occasion, for example outdoor operation of spraying method on the spot.

In the another embodiment of the present invention, rigid urethane foam can be by the preparation of each component mixture, at least a polyether glycol that it further comprises 3-20 part, have minimum functionality and be 2 and hydroxyl value be 150-600.

In order to realize purpose of the present invention, polyether glycol is preferably selected from aliphatic series or the aromatic polyol that molecular weight is 150-1600, and is made by the initiator with at least two sour hydrogen atoms and chain extender usually, is generally oxyethane or propylene oxide.

Wherein, Shi Yi polyether glycol has following structural formula:

Wherein, n is the integer of 1-20.

Preferably, it is 3-8 that polyether glycol has average functionality, and is short chain, and it is prepared by chain initiator, chain initiator is selected from glycerine, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, 1, tolylene diamine, sorbyl alcohol, sucrose and mannich base.

Rigid urethane foam prescription of the present invention below is described in detail in detail, and according to the hydroxy number of himself, polyether glycol has following function:

I) make porous plastics crosslinked and harmless fast, and adjusted the final viscosity of mixture in the operate continuously process final mechanical property,

Ii) adjust each component mixture rheological (flowability) and form duricrust or internal cavity and crosslinking time in the batch production process to reduce, and last

Iii) can satisfy the required dimensional stability requirement under differing temps of urethane foam under the different application condition.

In the prescription of rigid urethane foam of the present invention, the functionality of described polyether glycol be 3 and hydroxyl value be 100-230, preferably be about 160, have flow effect preferably when porous plastics forms, this is useful especially for continuous processing, batch method and spraying method.

In another embodiment of the present invention, special if desired resistivity against fire, when for example being used for the thermal isolation sheet material of heat ventilation or air-conditioning system usefulness pipeline, described rigid urethane foam can be made by described each component mixture, this mixture further comprises at least a halogenation or the phosphorated polyvalent alcohol of 5-10 part, its have minimum functionality be 2 and hydroxyl value be 200-400, more preferably 250-300.

In order to realize the object of the invention, the preferred halogenation polyvalent alcohol that uses is selected from the bromo polyvalent alcohol, and its viscosity is about 3000-11000mPa*s in the time of 25 ℃, 4000-6000mPa*s more preferably, and to have average functionality be 2-4.

Because this functionality is low, the preferred bromo polyvalent alcohol that uses makes urethane foam keep the plasticity-and the workability of required scope.

If resistivity against fire requires strict especially, preferably and valuably add the suitable fire retardant of 4-10 part to described each component starting mixt.

In order to realize the object of the invention, preferred fire retardant is selected from chlorinated phosphate as three (2-chloropropyl) phosphoric acid ester; Three (2-chloroethyl) phosphoric acid ester; Three (2,3-two chloropropyls) phosphoric acid ester; Four (2-chloroethyls)-2,2-two (chloromethyl) propyl phosphate; Dimethyl phosphate; Three (polyoxyalkylene glycol) phosphoric acid ester and three (polyoxyalkylene glycol) phosphorous acid ester; Three (chloro polyvalent alcohol) phosphoric acid ester; Two bromo dimethyltrimethylene glycols; Polyester bromo glycol and polyethers bromo glycol; Tetrabromo biphenol A; The phenyl tetrabromide dicarboxylic acid anhydride; Ammonium salt; Aluminium hydroxide; Trimeric cyanamide; Lime carbonate, and composition thereof.

Preferably, fire retardant is selected from those decomposition temperatures and is higher than 150 ℃, for example three (2-chloropropyl) phosphoric acid ester or three (2,3-two chloropropyls) phosphoric acid ester.

Independently, a back technical characterictic of fire retardant can help to reduce the viscosity of each component mixture, and not weaken the dimensional stability of prepared urethane foam by regulating final plasticity-.

In the preferred embodiments of the present invention, the differential responses that take place in the urethane foam preparation process are accelerated, and each reaction balances each other with the porous plastics of preparation desired properties, described initial each component mixture further comprises a at least catalyzer of 0-3 part, and it is selected from suitable kicker, polymerizing catalyst and catalyst for trimerization.

Within the scope of the invention, term " kicker " is illustrated in active catalyzer in water/isocyanate reaction; They are preferably selected from aliphatic series or cyclic aliphatic tertiary amine, aliphatic series or cyclic aliphatic ether amine, with and composition thereof.

Within the scope of the invention, term " polymerizing catalyst " is illustrated in active catalyzer in isocyanic ester/polyol reaction; They are preferably selected from aliphatic series or cyclic aliphatic tertiary amine, Sn ⁺⁺Salt, with and composition thereof.

Within the scope of the invention, term " catalyst for trimerization " is illustrated in the isocyanate trimerization reaction and generates active catalyzer in the isocyanines urea acid esters, because the high reaction activity of isocyanuric acid, isocyanuric acid ester makes the mechanical property and the thermotolerance of final urethane foam, and resistivity against fire improves in other words.

The preferred catalyst for trimerization that uses is selected from aliphatic series or cyclic aliphatic tertiary amine, lipid acid alkalescence salt, with and composition thereof.

What deserves to be mentioned is that the preferred tertiary amine that uses (can only by exemplifying) is selected from N, N-dimethylaminoethanol; N, the N-dimethylcyclohexylamine; Two (2-methylamino-ethyl) ether; N, N, N ', N ', N " pentamethyl--diethylidene-triamine; N, the N-dimethyl benzylamine; N, N-dimethyl cetylamine; Diamino bicyclooctane (DABCO); N-ethylmorpholine; Methylene radical-two-dimethylcyclohexylamine; N, N, N ', N ", N " pentamethyl--dipropylene-triamine; N, N '-diethyl piperazine; N, N, N '-front three amino-ethyl-thanomin; 1-(2-hydroxypropyl) imidazoles; 1,4-two (2-hydroxypropyl)-2-methylpiperazine.

Except said components, the starting mixt that the present invention prepares urethane foam can contain other possible non-crosslinked agent, for example, strengthens weighting agent or tinting material, and it can make urethane foam possess required performance.

In addition, the consumption of each component is all with reference to the definite easily ratio of those of ordinary skill in the art.

Following Table I indefiniteness represents that the composition of many each component mixtures generally can be used for preparing urethane foam of the present invention, according to coating process, i.e. and continuous processing, batch method and spraying method preparation.

In described table, unless stated otherwise, be weight part.

In the preferred embodiment of rigid urethane foam of the present invention and in the field of continuous coated method, need not transform conventional device, need only adopt each component mixture can obtain splendid composite sheet production rate, per each component mixture of 100 weight parts comprises:

At least a polyester polyol of-15-25 part, its have minimum functionality be 2 and hydroxyl value be 350-520, more preferably 350-500;

At least a isocyanate compound of-55-65 part, it has minimal index is 1.2 (120);

The bromo polyvalent alcohol of-4-8 part;

The polyamines that one of-1-3 part is aforementioned;

The water of-1.4-2 part;

-0.7 part silica-based surfactant.

More preferably, described rigid urethane foam can be by following embodiment preparation, and soon each component mixture foams simultaneously through reaction and prepares, and per each component mixture of 100 weight parts comprises:

At least a polyester polyol of-9-12 part, its have minimum functionality be 3 and hydroxyl value be about 500;

-7 parts at least a polyester polyol, its have minimum functionality be 3 and hydroxyl value be about 350.

Preferably, aforementioned isocyanate compound is " natural MDI " type, and isocyanate index is 1.4 (140)-1.5 (150).

Preferably, each component mixture of aforementioned per 100 weight parts comprises 6 parts of bromo polyvalent alcohols.

Preferably and in order further to improve the binding property of urethane foam to its support base, valuably, can use the following polyether glycol of 8 weight parts in per 100 weight part mixtures, and be preferably 6 parts, its hydroxy number is 160; And it is 1 part at least a catalyzer that maximum is arranged approximately.

Preferably, if having only a kind of catalyzer to exist, aforesaid each component mixture can comprise:

The amino catalyzer of-0-1 part, it is active (kicker) in isocyanic ester/water reaction; And/or

The amino catalyzer of-0-1 part, it is active (polymerizing catalyst) in isocyanic ester/polyol reaction; And/or

-0.5-1.5 part catalyzer, it is active (catalyst for trimerization) in the isocyanate trimerization reaction.

In order further to improve the resistivity against fire of urethane foam, valuably, can use other component-fire retardant, per 100 its maximums of weight part mixture are 8 parts, preferably are about 7 parts.

According to a further aspect in the invention, provide at least a heat insulating construction element, it comprises that at least one support base is connected in above-mentioned rigid urethane foam.

The heat insulating construction element that contains or be lined with described porous plastics can be, such as be used to prepare heat is ventilated or air-conditioning system with composite sheet, the curtain wall of pipeline, be used to make civilian or industrial building coiled material; Suitably be lined with the thermal insulating material of described porous plastics,, or be used for the wall of civilian or industrial building such as the wall that is used for refrigerating installation or refrigerating chamber.

Among the embodiment, material of construction of the present invention is essentially the sandwich-type composite structure, and it comprises a pair of support base that is folded with described rigid urethane foam therebetween.

Be used to make that heat is ventilated or the prefabricated thin-wall of the pipeline that air-conditioning system is used is the preferred embodiment of sandwich-type material of construction.

According to specific embodiment, manufacture method and prepared material of construction, rigidity or toughness sheet material that the optional free metal of described support base, concrete layer, brick, plank, plaster board and analogue etc. are made.

If the polyurethane foam layer in the material of construction only is connected with a support base; for example carry out the spraying method operation in the construction site; preferably and valuably, be provided with protective membrane with respect to a side of support base, avoid the infringement of weather with the protection porous plastics at rigid urethane foam.

In accordance with a further aspect of the present invention, provide a kind of method for preparing heat insulating construction element, described material comprises that at least a support base is connected on the rigid urethane foam with the form of thin plate, sheet material or sheet material, and this method may further comprise the steps:

A) provide the support base of a kind of thin plate, sheet material or sheet material form;

B) on described support base, add a certain amount of each above-mentioned component mixture;

C) described each component mixture crosslinked and foaming of process simultaneously, thus acquisition is connected in the rigid urethane foam of described substrate.

Preferably, method of the present invention further comprises step: before carrying out described each component mixture feed step, be provided with enhancing viscous layer (priming paint) on described support base.

Preferably, described priming paint is made up of conventional Resins, epoxy or vibrin, and it has fusible function between the urethane foam of improvement and support base.

Among the embodiment, method of the present invention further comprises step: the coated substrate in the described step c) is connected to established rigid urethane foam, thereby obtain to be essentially the material of construction of sandwich-type composite structure, it can be to be used to make such as heat and ventilates or the sheet material of the pipeline that air-conditioning system is used.

In order to increase the throughput of equipment, reduce cost the step a) described in the inventive method-c) all on known method and device, carry out continuously.

In the preferred embodiment, adopt quantitatively to mix in advance and be called " whipping agent "-e Foerderanlage in each component-prior art and realize this continuous processing, it both can be low-pressure type (this term finger pressure power is 0-15bar), also can be high-pressure type (this term finger pressure power is 100-200bar).

Under any situation, preferably the temperature of each component mixture is 20-28 ℃, and support base or lining preferably remain on 35-45 ℃ simultaneously.

Valuably,, can obtain higher composite architectural materials production rate, therefore reduce production cost thereby need not transform existing apparatus owing to adopt each above-mentioned component mixture.

Among another embodiment, a kind of method of producing the heat insulating construction element of sandwich-type composite structure in batches has been described, this structure is to be folded with described rigid urethane foam between a pair of support base, said method comprising the steps of:

A) the space certain distance is provided with the support base of a pair of thin plate, sheet material or sheet material form in shaped device;

B) add a certain amount of above-mentioned each component mixture between a pair of support base in described shaped device;

C) described each component mixture crosslinked and foaming of process simultaneously, thus acquisition is located in the rigid urethane foam between a pair of support base.

In order to realize the object of the invention, the method of described batch process heat insulating construction element can realize by adopting the shaped device that can reach this purpose, mould for example, its setting size that is fixed into die cavity is corresponding to the material of construction of being produced, or is equiped with the extrusion machine corresponding to the various size forming cavity of the material of construction of being produced.

In this case, preferred described method further comprises step: before carrying out described step b), use enhancing viscous layer (priming paint) on one in described a pair of support base.

In the preferred embodiment, adopt the feeding device that quantitatively mixes each component in advance to realize this continuous processing, it both can be low-pressure type (this term finger pressure power is 0-15bar), also can be high-pressure type (this term finger pressure power is 100-200bar).

Under any situation, preferably the temperature of each component mixture is 20-25 ℃, and support base or lining remain on 35-45 ℃ simultaneously.

Among another embodiment, a kind of method of producing heat insulating construction element, described material has at least one support base to be connected in described rigid urethane foam, and it can be realized by each crosslinked component mixture injection-coating, said method comprising the steps of:

A) a certain amount of above-mentioned each component mixture of spraying on described support base;

B) described each component mixture crosslinked and foaming of process simultaneously, thus acquisition is connected in the rigid urethane foam of described substrate.

Preferably; method of the present invention further comprises step: be provided with protective membrane at rigid urethane foam with respect to a side of support base; thereby in all embodiments, avoid urethane foam to be exposed in the air, realize useful sky gas shiled effect.

Then, still in this case, preferred described method further comprises step: before carrying out described step b), be provided with enhancing viscous layer (priming paint) on described support base.

In the preferred embodiments of the present invention, adopt a kind of whipping agent to realize spray technology, it both can be low-pressure type (this term finger pressure power is 0-15bar), also can be high-pressure type (this term finger pressure power is 100-200bar).

Under any situation, preferably the temperature of each component mixture is 30-70 ℃, and simultaneously according to residing envrionment conditions, the temperature range of support base is minimum 5 ℃ and arrives the highest 45 ℃.

The manufacturing process of the urethane foam of realizing with continuous processing, batch method and spraying method described in the present invention, can produce more complicated compound heat insulating construction element, this technology can realize on known device, for example, as described in George Woods, see " The ICIPolyurethanes Book ", second edition, ICI Polyurethanes and John Wiley ﹠amp; Sons, 1990.

Reach in accordance with a further aspect of the present invention in order to simplify the production technique of urethane foam, also be provided for preparing a kind of liquid catalyst composition of rigid urethane foam at last,

It comprises:

-at least a liquid vehicle is selected from polyester polyol, polyether glycol, halogenation or phosphorated polyvalent alcohol and fire retardant, and viscosity is 10-300mPa*s in the time of 25 ℃;

-the polyamines that is shown below

Wherein n is the integer of 1-20;

-at least a catalyzer is selected from suitable kicker, polymerizing catalyst and catalyst for trimerization.

In the preferred embodiment, described polyester polyol, polyether glycol, halogenation or phosphorated polyvalent alcohol and fire retardant are all as described above.

Valuably, this type of liquid composition can obtain intermediate product all useful in any production process, and it makes some component in the reaction mixture predeterminable quantitatively, thereby makes the foaming of quantitative work and porous plastics and crosslinked operation easier.

In addition, under the situation that described diamines exists, catalyst composition of the present invention has improved the binding property of porous plastics to its support base valuably, and requires not too harsh to the feed and the control of process parameters in the foaming step of reagent.

In order to realize the object of the invention, the liquid catalyst composition preferably includes the various components of measuring described in following Table II.

As shown in Table II, preferably and valuably, each component in the catalyst composition adopts the consumption shown in the table.

	Production technique
				Component	Continuous processing	Batch method	Spraying method

Carrier	78-82	74-78	50-54
				Polyamines	13-18	18-22	22-28
The catalyzer total amount	4-6	2-4	20-25
				Kicker	0.1-0.3	0.6-1.0	4-8
Polymerizing catalyst	2.0-2.5	1.0-1.5	8.0-9.0
				Catalyst for trimerization	2.0-2.5	1.8-2.2	8.5-9.0

By the following embodiment of urethane foam of the present invention, further characteristics of the present invention and advantage will be more apparent, and described embodiment right and wrong are determinate.Among the embodiment, unless specialize, the umber of each component is weight part.

Embodiment 1

(the present invention)

First kind of heat insulating construction element prepares by continuous processing, and it is made up of composite sheet, has sandwich type structure, and this structure is formed by two fine aluminium sheet materials that are folded with the urethane foam interposed layer.

The mixture that is adopted comprises following compositions:

-commercially available polyester polyol have average functionality be 3 and hydroxy number be 400-600, trade mark is called ISOEXTER ^TM(C.O.I.M.S.p.A., Settimo Milanese, Milan, Italy makes);

-commercially available polyester polyol have average functionality be 3 and hydroxy number be 300-400, trade mark is called ISOEXTER ^TM(C.O.I.M.S.p.A. manufacturing);

-commercially available polyether glycol have average functionality be 3 and hydroxy number be 100-300, trade mark is called TERCAROL ^TM(Italy makes for ENICHEM.S.p.A., Milan);

-commercially available bromo polyvalent alcohol have average functionality be 2 and hydroxy number be 250-300, trade mark is called AROFLAM ^TM(ENICHEM.S.p.A. manufacturing);

-whipping agent=water;

-commercially available fire retardant=trichlorine propyl phosphate (TCPP);

-commercially available silica-based surfactant=DABCO DC193 (AIRPRODUCTS, Allentown, PA, U.S.A. manufacturing);

-commercially available kicker=N, " pentamethyl--diethylidene-triamine, trade mark is called POLYCAT for N, N ', N ', N ^TM5 (AIR PRODUCTS manufacturings);

-commercially available polymerizing catalyst=N, the N-dimethylcyclohexylamine, trade mark is called POLYCAT ^TM8 (AIR PRODUCTS manufacturings);

-commercially available catalyst for trimerization=commercially available trade mark CATALIST LB by name (Italy makes for ICIITALIA, Ternate);

-commercially available the diamines shown in the formula V as described above;

-commercially available isocyanate compound=commercially available polymeric MDI trade mark SUPRASEC (ICI ITALIA manufacturing) by name.

Described mixture adds and is dispersed on the first embossing fine aluminium sheet material of the about 80 μ m of thickness, adopts conventional whipping agent, and is commercially available, and trade mark is called AFROS CANNON (Italy makes for Caronno Pertusella, Varese).

In quantitative step, each component keeps when temperature is about 25 ℃ and feeds.

To each component in the porous plastics reaction/foaming step in the roller mill quantitatively after, adopt ordinary method and device can realize the present invention, described roller mill comprises two low sides and two high-end rotary conveyors, is set parallel to each other.

Subsequently, second aluminum sheet, i.e. the upper strata of described composite sheet feeds roller mill in as hereinbefore mode.

In urethane foam moulding/foaming step, it is 40 ℃ of temperature that rotary conveyor is maintained at about, and adjusts their transfer rate simultaneously, makes porous plastics whole residence time of moulding/foaming in roller mill be about 3 minutes.

In addition, adjusting distance between two rotary conveyors satisfies final composite sheet thickness and is about 2cm.

In the outlet of shaping channel, obtain successive composite sheet basically, it is stored after cutting via conventional cutting facility.

Be used to prepare shown in the following Table III of component of each component mixture of porous plastics.

Embodiment 2

(the present invention)

Second kind of heat insulating construction element prepares by batch method, and it is made up of composite sheet, has sandwich type structure, and this structure is formed by two steel boards that are folded with the urethane foam interposed layer.

The reaction mixture that is adopted comprises following compositions:

-polyester polyol have average functionality be 3 and hydroxy number be 300-400, commercially available, trade mark is called ISOEXTER ^TM(C.O.I.M.S.p.A. manufacturing);

-polyether glycol have average functionality be 5 and hydroxy number be 450-550, commercially available, trade mark is called CARADOL ^TM520 (Italy makes for SHELL ITALIA, Milan);

-polyether glycol have average functionality be 3 and hydroxy number be 100-300, commercially available, trade mark is called TERCAROL ^TM1 (ENICHEM.S.p.A. manufacturing);

-whipping agent=water;

-fire retardant=trichlorine propyl phosphate (TCPP), commercially available;

-silica-based surfactant=DABCO DC193 (AIR PRODUCTS manufacturing);

-kicker=N, " pentamethyl--diethylidene-triamine, commercially available, trade mark is called POLYCAT for N, N ', N ', N ^TM5 (AIR PRODUCTS manufacturings);

-catalyst for trimerization=commercially available, trade mark are called CATALIST LB (ICI ITALIA manufacturing);

-the diamines shown in the formula V as described above, commercially available;

-isocyanate compound=polymeric MDI, commercially available, trade mark is called SUPRASEC (ICIITALIA manufacturing).

Described mixture adds and is dispersed on the steel board of the about 600 μ m of a pair of thickness, and it is supported in the mould to preset spacing, adopts conventional whipping agent, and Hennecke GmbH (SanktAugustin, Germany) on sale.

In quantitative step, each component keeps when temperature is about 25 ℃ and feeds.

To each component in reaction/foaming step of being located at porous plastics in the mould molding chamber quantitatively after, wherein sheet material is arranged in parallel, to each other apart from being about 5cm, thereby the urethane foam of preparation respective thickness.

In urethane foam moulding/foaming step, sheet material remains on temperature and is about 40 ℃, and porous plastics is about 20 minutes in whole residence time of die for molding/foaming simultaneously.

Be used to prepare shown in the following Table III of component of each component mixture of porous plastics.

Embodiment 3

(the present invention)

The third heat insulating construction element prepares by spraying method, and it is made up of the coiled material that the steel board of the about 600 μ m of thickness makes, and is lined with polyurethane foam layer on the sheet material.

The reaction mixture that is adopted comprises following compositions:

-polyester polyol have average functionality be 3 and hydroxy number be 400-600, commercially available, trade mark is called ISOEXTER ^TM(C.O.I.M.S.p.A. manufacturing);

-polyester polyol have average functionality be 3 and hydroxy number be 300-400, commercially available, trade mark is called ISOEXTER ^TM(C.O.I.M.S.p.A. manufacturing);

-polyester polyol have average functionality be 4 and hydroxy number be 300-400, commercially available, trade mark is called ISOEXTER ^TM(C.O.I.M.S.p.A. manufacturing);

-polyether glycol have average functionality be 3 and hydroxy number be 100-300, commercially available, trade mark is called TERCAROL ^TM1 (ENICHEM.S.p.A. manufacturing);

-whipping agent=water;

-fire retardant=trichlorine propyl phosphate (TCPP), commercially available;

-silica-based surfactant=DABCO DC193 (AIR PRODUCTS, ALLentowm, PA, U.S.A. makes);

-kicker=N, " pentamethyl--diethylidene-triamine, commercially available, trade mark is called POLYCAT for N, N ', N ', N ^TM5 (AIR PRODUCTS manufacturings);

-polymerizing catalyst=N, the N-dimethylcyclohexylamine, commercially available, trade mark is called POLYCAT ^TM8 (AIR PRODUCTS manufacturings);

-catalyst for trimerization=commercially available, trade mark are called CATALIST LB (ICI ITALIA manufacturing);

-the diamines shown in the formula V as described above, commercially available;

-isocyanate compound=polymeric MDI, commercially available, trade mark is called SUPRASEC (ICIITALIA manufacturing).

Described mixture at first is sprayed on the coiled material, adopts conventional whipping agent, Gusmer (Lakewood, NJ, U.S.A.) on sale, with after crosslinked and simultaneously the foaming, make the rigid urethane foam that is connected in support base.

In quantitative step, each component keeps when temperature is about 30 ℃ and feeds, and is sprayed at the temperature of sheet material corresponding to each component.

To each component in the reaction/expansion step of porous plastics quantitatively after, porous plastics is positioned in the air and externally (30 ℃) under the temperature, makes the polyurethane foam layer that thickness is about 4cm.

The full time that porous plastics is finished moulding/foaming is about 1 minute.

Be used to prepare shown in the following Table III of component of each component mixture of porous plastics.

Embodiment 4a-4c

(comparative example)

According to method in the previous embodiment 1 and device, three kinds of similar heat insulating construction elements of material of construction layer fully and among the embodiment 1 are prepared by continuous processing, described three kinds of materials are made up of multiple composite sheet, have sandwich type structure, this structure is formed by two fine aluminium sheet materials that are folded with the urethane foam interposed layer.

In this case, the mixture that is adopted comprises following compositions:

-polyether glycol have average functionality be 4.5 and hydroxy number be 500, commercially available, trade mark is called GLENDION ^TMRS0700 (ENICHEM.S.p.A. manufacturing) [embodiment 4a-4c];

-polyether glycol have average functionality be 5 and hydroxy number be 530, commercially available, trade mark is called CARADOL ^TM530 (SHELL ITALIA manufacturing) [embodiment 4a-4c];

-polyether glycol have average functionality be 3 and hydroxy number be 160, commercially available, trade mark is called TERCAROL ^TM1 (ENICHEM.S.p.A. manufacturing) [embodiment 4c];

-fire retardant=trichlorine propyl phosphate (TCPP), commercially available, [embodiment 4a-4c];

-linking agent=glycerine, commercially available, [embodiment 4a and 4b];

-silica-based surfactant=DABCO DC193 (AIR PRODUCTS manufacturing) [embodiment 4a-4c];

-kicker=N, " pentamethyl--diethylidene-triamine, commercially available, trade mark is called POLYCAT for N, N ', N ', N ^TM5 (AIR PRODUCTS manufacturing) [embodiment 4c];

-polymerizing catalyst=N, the N-dimethylcyclohexylamine, commercially available, trade mark is called POLYCAT ^TM8 (AIR PRODUCTS manufacturing) [embodiment 4a and 4b];

-catalyst for trimerization=commercially available, trade mark are called CATALIST LB (ICI IATLIA manufacturing) [embodiment 4a-4c];

-isocyanate compound=polymeric MDI, commercially available, trade mark is called SUPRASEC (ICIITALIA manufacturing) [embodiment 4a-4c].

Used whipping agent is as follows respectively:

-hydrogenated chloride fluorine hydrocarbon, commercially available, industry 141b[embodiment 4a by name];

-Skellysolve A [embodiment 4b];

-water [embodiment 4c].

In the prescription of embodiment 4a and 4b, a spot of water impels the rapid expansion of porous plastics as auxiliary blowing agent.

Be used to prepare shown in the following Table IV of component of each component mixture of porous plastics.

Embodiment 5a-5c

(comparative example)

According to method in the previous embodiment 2 and device, three kinds fully with embodiment 2 in the similar heat insulating construction element of layer of material of construction prepare by batch method, described three kinds of materials are made up of multiple composite sheet, have sandwich type structure, this structure is formed by two steel boards that are folded with the urethane foam interposed layer.

In this case, the mixture that is adopted comprises following compositions:

-polyether glycol have average functionality be 4.5 and hydroxy number be 500, commercially available, trade mark is called GLENDION ^TMRS0700 (ENICHEM.S.p.A. manufacturing) [embodiment 5a-5c];

-polyether glycol have average functionality be 3 and hydroxy number be 160, commercially available, trade mark is called TERCAROL ^TM1 (ENICHEM S.p.A. manufacturing) [embodiment 5a-5c];

-fire retardant=trichlorine propyl phosphate (TCPP), commercially available [embodiment 5a-5c];

-silica-based surfactant=DABCO DC193 (AIR PRODUCTS manufacturing) [embodiment 5a-5c];

-kicker=N, " pentamethyl--diethylidene-triamine, commercially available, trade mark is called POLYCAT for N, N ', N ', N ^TM5 (AIR PRODUCTS manufacturing) [embodiment 5c];

-polymerizing catalyst=N, the N-dimethylcyclohexylamine, commercially available, trade mark is called POLYCAT ^TM8 (AIR PRODUCTS manufacturing) [embodiment 5a-5c];

-isocyanate compound=polymeric MDI, commercially available, trade mark is called SUPRASEC (ICIITALIA manufacturing) [embodiment 5a-5c].

Whipping agent is as follows respectively:

-hydrogenated chloride fluorine hydrocarbon, commercially available, industry 141b[embodiment 5a by name];

-Skellysolve A [embodiment 5b];

-water [embodiment 5c].

Similarly, in the prescription of embodiment 5a and 5b, a spot of water impels the rapid expansion of porous plastics as auxiliary blowing agent.

Be used to prepare shown in the following Table IV of component of each component mixture of porous plastics.

Embodiment 6

(comparative example)

According to method in the previous embodiment 3 and device, prepare a kind of similar heat insulating construction element of material of construction layer fully and among the embodiment 3, described heat insulating construction element is made up of the steel board that is lined with polyurethane foam layer.

In this case, the mixture that is adopted comprises following compositions:

-polyether glycol have average functionality be 5 and hydroxy number be 530, commercially available, trade mark is called CARADOL ^TM530 (SHELL ITALIA manufacturings);

-polyether glycol have average functionality be 3 and hydroxy number be 160, commercially available, trade mark is called TERCAROL ^TM1 (ENICHEM.S.p.A. manufacturing);

-polyester polyol have average functionality be 2 and hydroxy number be 250, commercially available, trade mark is called STEPANPOL ^TMRS0700 (U.S.A. makes for STEPAN COMPANY, Illinois);

-fire retardant=trichlorine propyl phosphate (TCPP), commercially available;

-linking agent=glycerine, commercially available;

-silica-based surfactant=DABCO DC193 (AIR PRODUCTS manufacturing);

-kicker=N, " pentamethyl--diethylidene-triamine, commercially available, trade mark is called POLYCAT for N, N ', N ', N ^TM5 (AIR PRODUCTS manufacturings);

-polymerizing catalyst=N, the N-dimethylcyclohexylamine, commercially available, trade mark is called POLYCAT ^TM8 (AIR PRODUCTS manufacturings);

-catalyst for trimerization=commercially available, trade mark is called CATALIST LB (ICI IATLIA);

-isocyanate compound=polymeric MDI, commercially available, trade mark is called SUPRASEC (ICIITALIA manufacturing).

Whipping agent is the hydrogenated chloride fluorine hydrocarbon, and is commercially available, industry 141b by name.Similarly, in the present embodiment, a spot of water impels the rapid expansion of porous plastics as auxiliary blowing agent.

Be used to prepare shown in the following Table IV of component of each component mixture of porous plastics.

Embodiment 7

(porous plastics density is determined)

Urethane foam sample among embodiment 1-3 (the present invention), 4a-4c, the 5a-5c and 6 (comparative example) carries out the test of a series of definite foam plastics core volume densitys.

Described test secundum legem EN1602 carries out.

Test result is shown in down Table V, VI and VII, and it is respectively the product by continuous processing (embodiment 1,4a-c), batch method (embodiment 2,5a-c) and spraying method (embodiment 3,6) preparation.

Detected result shows, no matter is at continuous processing or batch method or spraying method, and the core body density value of urethane foam of the present invention (embodiment 1-3) all is higher than porous plastics of the prior art (embodiment 4a-4c, 5a-5c and 6).

Embodiment 8

(the porous plastics heat conductivity is determined)

Urethane foam sample among embodiment 1-3 (the present invention), 4a-4c, the 5a-5c and 6 (comparative example) carries out the test of a series of definite porous plastics heat conductivities.

Described test secundum legem UNI7891 carries out.

Test result is shown in down Table V, VI and VII, and it is respectively the product by continuous processing (embodiment 1,4a-c), batch method (embodiment 2,5a-c) and spraying method (embodiment 3,6) preparation.

Detected result shows, no matter is at continuous processing or batch method or spraying method, and the thermal conductivity of urethane foam of the present invention (embodiment 1-3) and porous plastics of the prior art (embodiment 4a-4c, 5a-5c and 6) are similar.

Embodiment 9

(the porous plastics dimensional stability is determined during temperature variation)

The test of porous plastics dimensional stability when the urethane foam sample among embodiment 1-3 (the present invention), 4a-4c, the 5a-5c and 6 (comparative example) carries out a series of definite temperature variation.

Described test secundum legem EN1604 carries out.

Test result is shown in down Table V, VI and VII, and it is respectively the product by continuous processing (embodiment 1,4a-c), batch method (embodiment 2,5a-c) and spraying method (embodiment 3,6) preparation.

Detected result shows when temperature is-25 ℃, no matter adopt continuous processing or batch method, and the dimensional stability of urethane foam of the present invention (embodiment 1-2) and porous plastics of the prior art (embodiment 4a-4c and 5a-5c) are similar; And in the time of 70 ℃, the dimensional stability of urethane foam of the present invention (embodiment 1-2) significantly is better than with water as the urethane foam (embodiment 4c and 5c) of whipping agent and near with 141b and the Skellysolve A porous plastics (embodiment 4a-4b and 5a-5b) as whipping agent.

In the example of spraying method, the dimensional stability of urethane foam of the present invention (embodiment 3) is near porous plastics of the prior art (embodiment 6).

Embodiment 10

(resistivity against fire is determined)

Urethane foam sample among embodiment 1-3 (the present invention), 4a-4c, the 5a-5c and 6 (comparative example) carries out the test of a series of definite porous plastics resistivity against fires.

Described test secundum legem DIN 4102 carries out.

Test result is shown in down Table V, VI and VII, and it is respectively the product by continuous processing (embodiment 1,4a-c), batch method (embodiment 2,5a-c) and spraying method (embodiment 3,6) preparation.

According to aforesaid standards, porous plastics is divided into three ranks, B1, B2 and B3 according to the reaction to fire in experiment.B1 rank porous plastics has shown experimental result preferably, and the porous plastics experimental result is the poorest in the B3 rank.

Detected result shows, no matter is at continuous processing or batch method or spraying method, and the resistivity against fire of urethane foam of the present invention (embodiment 1-3) is better than porous plastics of the prior art (embodiment 4a-4c, 5a-5c and 6).

Embodiment 11

(porous plastics is determined its support base is fusible)

Urethane foam sample among embodiment 1-3 (the present invention), 4a-4c, the 5a-5c and 6 (comparative example) carries out a series of definite porous plastics to the fusible test of its support base.

Described test secundum legem EN 1607 carries out.

Test result is shown in down Table V, VI and VII, and it is respectively the product by continuous processing (embodiment 1,4a-4c), batch method (embodiment 2,5a-5c) and spraying method (embodiment 3 and 6) preparation.

Detected result shows, no matter adopt continuous processing or batch method, urethane foam of the present invention (embodiment 1-2) is better than porous plastics of the prior art (embodiment 4 and 5) to the binding property of its support base, and is better than especially with the porous plastics (embodiment 4c and 5c) of water as whipping agent.

In the example of spraying method, urethane foam of the present invention (embodiment 3) is to the approaching porous plastics of the prior art (embodiment 6) of the binding property of its support base.

Table I

	Production technique
				Component	Continuous processing	Batch method	Spraying method
Polyester polyol F=3 OH=400-600	8-10	-	5-10
				Polyester polyol F=3 OH=300-400	6-10	10-20	10-15
Polyester polyol F=4 OH=300-400	-	-	2-3
				Polyether glycol F=5 OH=450-550	-	5-10	-
Polyether glycol F=3 OH=100-300	3-7	5-10	2-3
				Bromo polyvalent alcohol F=2 OH=250-300	6-10	-	-
Water	1-1.5	1.4-1.8	1.2-1.6
				Fire retardant	4-10	6-10	5-10
Silica-based surfactant	0.5-0.8	0.6-0.9	0.5-1
				Kicker	0.02-0.1	0-0.1	0.3-1
Polymerizing catalyst	0.1-0.2	-	0.3-1.5
				Catalyst for trimerization	0.1-0.4	0.05-0.2	0.3-1.5
Polyamines	0.1-2	1-3	1.5-4
				Isocyanate compound	55-65	50-60	52-62

The F=average functionality

OH=hydroxy number [mgKOH/g]

Table II

	Production technique
				Component	Continuous processing	Batch method	Spraying method
Carrier	70-90	70-80	45-70
				Polyamines	10-20	15-30	20-30
The catalyzer total amount	3-8	2-5	20-30
				Kicker	0.1-0.5	0.5-1.0	3-10
Polymerizing catalyst	1.8-3.0	0.8-2.0	6-15
				Catalyst for trimerization	1.5-3.0	1-3	6-12

Table III

Component	Embodiment 1 *	Embodiment 2 *	Embodiment 3 *
				Polyester polyol F=3 OH=400-600	9	-	8
Polyester polyol F=3 OH=300-400	7	15	13
				Polyester polyol F=4 OH=300-400	-	-	2.5
Polyether glycol F=5 OH=450-550	-	9	-
				Polyether glycol F=3 OH=100-300	5	6	2.5
Bromo polyvalent alcohol F=2 OH=250-300	7	-	-
				Water	1.2	1.5	1.3
Fire retardant	9	9	8
				Silica-based surfactant	0.7	0.7	0.7
Kicker	0.05	0.07	0.7
				Polymerizing catalyst	0.15	-	1
Catalyst for trimerization	0.3	0.1	1
				Polyamines	1	1.5	3
Isocyanate compound	59.6	57.1	58.5

The F=average functionality

OH=hydroxy number [mgKOH/g]

^*=the present invention

Table IV

Component	Embodiment 4a **	Embodiment 4b **	Embodiment 4c **	Embodiment 5a **	Embodiment 5b **	Embodiment 5c **	Embodiment 6 **
								Polyether glycol F=4.5 OH=500	24	25	15	25	26.4	12.6	-
Polyether glycol F=5 OH=530	6.0	6.3	6.1	-	-	-	12.5
								Polyether glycol F=3 OH=160	-	-	9.2	6.3	6.6	18.9	7.5
Polyester polyol F=2 OH=250	-	-	-	-	-	-	5
								Water	0.45	0.47	1.4	0.47	0.5	1.6	0.3
Skellysolve A	-	4.7	-	-	5.95	-	-
								141b	8.5	-	-	11	-	-	8.75
Fire retardant	4.5	4.7	9.2	6.3	6.6	9.4	12.5
								Linking agent	0.9	0.94	-	-	-		0.75
Silica-based surfactant	0.6	0.62	0.61	0.6	0.66	0.6	0.5
								Kicker	-	-	0.5	-	-	0.2	0.5
Polymerizing catalyst	0.3	0.52	-	0.3	0.33	0.1	1.3
								Catalyst for trimerization	0.1	0.11	0.11	-	-	-	0.2
Isocyanate compound	54.5	56.6	57.9	50.0	53.0	56.6	50.2

The F=average functionality

OH=hydroxy number [mgKOH/g]

^*=comparative example

Table V

	The continuous processing production technique
					Performance	Embodiment 1 *	Embodiment 4a **	Embodiment 4b **	Embodiment 4c **
Density [kg/m 3]	40	35	35	33
					Thermal conductivity [W/m ℃]	0.025	0.020	0.025	0.027
Dimensional stability-25 ℃ [%]+70 ℃ [%]	0.2 2	0.5 3	0.5 3	0.2 10
					Light-off trial [DIN level]	B2	B3/B2	B3	B3
Binding property [kg/cm 2]	1.2	1	1	0.1

^*=the present invention ^*=comparative example

Table VI

	Mass production processes
					Performance	Embodiment 2 *	Embodiment 5a **	Embodiment 5b **	Embodiment 5c **
Density [kg/m 3]	40	35	35	33
					Thermal conductivity [W/m ℃]	0.025	0.020	0.025	0.027
Dimensional stability-25 ℃ [%]+70 ℃ [%]	0.5 2	1 3	1 3	0.5 15
					Light-off trial [DIN level]	B2	B3/B2	B3	B3
Binding property [kg/cm 2]	1.5	1.5	1.5	0.1

^*=the present invention ^*=comparative example

Table VII

	The spraying method production technique
			Performance	Embodiment 3 *	Embodiment 6 **
Density [kg/m 3]	40	35
			Thermal conductivity [W/m ℃]	0.025	0.020
Dimensional stability-25 ℃ [%]+70 ℃ [%]	0.2 2	0.2 2
			Light-off trial [DIN level]	B2	B3
Binding property [kg/cm 2]	1	1

^*=the present invention ^*=comparative example

Claims (25)

1. rigid urethane foam, it is a foaming structure, constitute by the closed porosity that does not contain non-essential halohydrocarbon foaming agent, described urethane foam obtains by the non-organic blowing agent that uses each component mixture, described mixture comprises water base whipping agent, at least a polyvalent alcohol and at least a isocyanate compound

Wherein said each component mixture does not comprise the carbon imide catalyzer that contains phosphine oxide alkene,

Reach described urethane foam support base is had bounding force, secundum legem EN1607 measures, and is equal to or higher than 0.7kg/cm ²

2. urethane foam as claimed in claim 1, wherein in minimum temperature-25 ℃ in the scope of 70 ℃ of top temperatures, secundum legem EN 1604 setting-out line size unevenness percentage ratios are not higher than 4%.

3. urethane foam as claimed in claim 1, the fragility measured of secundum legem ASTMC421 wherein, promptly weight loss percentage ratio is not higher than 3%.

4. urethane foam as claimed in claim 1, wherein the thermal conductivity of secundum legem ISO6902 mensuration is 0.024-0.028W/m ℃.

5. urethane foam as claimed in claim 1, per 100 weight parts of the mixture of wherein said each component comprise:

At least a polyester polyol of 10-25 part, its have minimum functionality be 2 and hydroxyl value be 250-600;

At least a isocyanate compound of 50-65 part;

The water base whipping agent of 1-2 part;

0.3-2 part appropriate surfactant, it makes described at least a polyvalent alcohol and described isocyanate compound miscible mutually.

6. as claim 1 or 5 described urethane foams, wherein said each component mixture further comprises the polyamines that is shown below of 0.1-4 weight part:

Wherein n is the integer of 1-20.

7. as claim 1 or 5 described urethane foams, wherein said each component mixture further comprises at least a polyether glycol of 3-20 part, its have minimum functionality be 2 and hydroxyl value be 150-550.

8. as each described urethane foam of claim 1～5, wherein said each component mixture further comprises at least a halo or the phosphorated polyvalent alcohol of 5-10 part, its have minimum functionality be 2 and hydroxyl value be 240-300.

9. as each described urethane foam of claim 1～5, wherein said each component mixture further comprises the fire retardant that 4-10 part is suitable.

10. as claim 1 or 5 described urethane foams, wherein said each component mixture further comprises the catalyzer of 0-3 part, it is selected from suitable kicker, polymerizing catalyst and catalyst for trimerization, contains except the carbon imide catalyzer of phosphine oxide alkene.

11. a heat insulating construction element, it comprises at least one support base, and described support base is connected in rigid urethane foam as claimed in claim 1.

12. material of construction as claimed in claim 11 is a kind of sandwich-type composite structure, it is included in and is folded with described rigid urethane foam between a pair of support base.

13. as claim 11 or 12 described material of construction, wherein said support base is selected from rigidity or the toughness sheet material of being made by metal, concrete layer, brick, plank, plaster board.

14. material of construction as claimed in claim 11 further is included in rigid urethane foam and is provided with protective membrane with respect to a side of support base.

15. material of construction as claimed in claim 12 is used for the pipeline that air-conditioning system is used with prefabricated thin-wall manufacturing.

16. a method for preparing heat insulating construction element, described material comprise that at least one support base is connected on the rigid urethane foam with the form of thin plate, sheet material or sheet material, this method may further comprise the steps:

A) provide the support base of a kind of thin plate, sheet material or sheet material form;

B) interpolation is a certain amount of according to described each component mixture of claim 5 on described support base;

C) described each component mixture crosslinked and foaming of process simultaneously, thus acquisition is connected in the rigid urethane foam of described substrate.

17. method as claimed in claim 16 further comprises step: be provided with protective membrane with respect to a side of support base at rigid urethane foam.

18. method as claimed in claim 16 further comprises step: carrying out on described support base, using priming paint before the described feed step.

19. method as claimed in claim 16 further comprises step: the coated substrate in the described step c) is connected in type rigid urethane foam, thereby obtains to be the material of construction of sandwich-type composite structure.

20. as arbitrary described method among the claim 16-19, wherein said step a)-c) all carry out continuously.

21. a method of producing heat insulating construction element in batches, described material are the sandwich-type composite structure, this structure is to be folded with described rigid urethane foam between a pair of support base, said method comprising the steps of:

A) the space certain distance is provided with the support base of a pair of thin plate, sheet material or sheet material form in shaped device;

B) interpolation is a certain amount of according to described each component mixture of claim 5 between a pair of support base in described shaped device;

C) described each component mixture crosslinked and foaming of process simultaneously, thus the rigid urethane foam between a pair of support base is located in acquisition.

22. method as claimed in claim 21 further comprises step: before carrying out described step b), use priming paint at least one in described a pair of support base.

23. a method of producing heat insulating construction element, described material have at least one support base to be connected in described rigid urethane foam, said method comprising the steps of:

A) a certain amount of each component mixture according to claim 5 of spraying on described support base;

B) described each component mixture crosslinked and foaming of process simultaneously, thus acquisition is connected in the rigid urethane foam of described substrate.

24. method as claimed in claim 23 further comprises step: be provided with protective membrane with respect to a side of support base at rigid urethane foam.

25. method as claimed in claim 23 further comprises step: before carrying out described spraying step, on described support base, use priming paint.